CN111212810A - System and method for supplying and further using hydrogen - Google Patents
System and method for supplying and further using hydrogen Download PDFInfo
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- CN111212810A CN111212810A CN201880065003.XA CN201880065003A CN111212810A CN 111212810 A CN111212810 A CN 111212810A CN 201880065003 A CN201880065003 A CN 201880065003A CN 111212810 A CN111212810 A CN 111212810A
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
- C01B3/50—Separation of hydrogen or hydrogen containing gases from gaseous mixtures, e.g. purification
- C01B3/501—Separation of hydrogen or hydrogen containing gases from gaseous mixtures, e.g. purification by diffusion
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
- C01B3/02—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen
- C01B3/22—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by decomposition of gaseous or liquid organic compounds
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
- C01B2203/04—Integrated processes for the production of hydrogen or synthesis gas containing a purification step for the hydrogen or the synthesis gas
- C01B2203/0405—Purification by membrane separation
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
- C01B2203/06—Integration with other chemical processes
- C01B2203/066—Integration with other chemical processes with fuel cells
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Abstract
The invention relates to a system for providing hydrogen, comprising a dehydrogenation unit (4) for releasing a hydrogen-containing gas mixture from an at least partially loaded hydrogen-carrying medium; a separation/purification unit (5) connected to the dehydrogenation unit (4) for at least partially separating hydrogen from the gas mixture and purifying the separated hydrogen, wherein the separation/purification unit (5) has a separation membrane (17); a utilization unit (6) connected to the separation/purification unit (5; 5a) for utilizing the purified hydrogen; a thermal conversion unit (7) connected to the separation/purification unit (5; 5a) for thermally converting the residual gas mixture.
Description
The present patent application claims priority from german patent application DE 102017217748.9, the contents of which are incorporated herein by reference.
The present invention relates to a system and method for supplying and further using hydrogen.
The hydrogen can be used for power generation in the fuel cell. For this purpose, hydrogen gas must be supplied in a high purity of, for example, at least 99.9%. Impurities such as carbon monoxide (CO) or hydrocarbons (TOC) are particularly undesirable and impair the operation of the fuel cell.
One known method for providing hydrogen is to dehydrogenate a hydrogen-carrying medium, in particular a liquid organic hydrogen-carrying medium, also known as Liquid Organic Hydrogen Carrier (LOHC). JP2002/134141A discloses the separation of hydrogen from a gas mixture by means of an LOHC dehydrogenation reaction. The separation of hydrogen using the LOHC dehydrogenation reaction is expensive, and thus the separated hydrogen should be used as much as possible for power generation. The maximum efficiency of the fuel cell is 55%. The overall efficiency is based on the fuel cell efficiency, the hydrogenation efficiency of the hydrogen-carrying medium of 98% and the dehydrogenation efficiency of the latter 70%, and is at most 38%. The actual efficiency of a fuel cell is typically between 45% and 50%, so the actual overall efficiency is about 30% to 34%.
The aim of the invention is to improve the supply of hydrogen, in particular for utilization in fuel cells, in particular to increase the efficiency to a theoretical maximum overall efficiency of 38%.
This object is achieved by a system having the features of claim 1 and a method having the features of claim 6. The core of the invention is that the hydrogen in the gas mixture from the dehydrogenation unit is at least partially separated and purified in a separation/purification unit. It has surprisingly been found that the overall efficiency of the process is increased if only a sub-stream of the gas mixture is purified for later use in power generation. The expenditure involved in the purification of the substreams to be used for power generation is reduced, thereby increasing the overall efficiency. This is particularly advantageous when the separation/purification unit has a separation membrane for separating hydrogen from a gas mixture and for purifying hydrogen. The present invention is also based on the discovery that: separation membranes can be used to purify hydrogen from the dehydrogenation of LOHC. According to the invention, a two-step process known from the prior art with an upstream separation step and a downstream purification step can be achieved as a combined one-step process by means of a separation membrane. The process is simplified and in particular the costs involved in hydrogen purification are reduced. The main advantage of the present invention is that the overall efficiency is improved while the expense involved in hydrogen purification is reduced.
If the hydrogen-carrying medium used is LOHC, hydrogen is released by catalytic dehydrogenation of organic molecules or mixtures of organic molecules. This means that hydrogen is released by physical transformation of the loaded support medium (unloading in the unloading unit by means of a catalytic dehydrogenation reaction). In the loaded state, the support medium is in particular a saturated polycyclic compound, in particular perhydrodibenzyltoluene or perhydrobenzyltoluene, which can be used as pure substances, isomer mixtures or mixtures with one another. Alternatively, the carrier medium to be loaded is a saturated polycyclic compound containing heteroatoms such as nitrogen or oxygen, in particular perhydro-N-ethylcarbazole, perhydro-N-propylcarbazole, perhydro-N-isopropylcarbazole, perhydro-N-butylcarbazole or a combination of these substances. Alternatively, the supporting support medium used may also be a saturated organic oligomer or polymer which can be converted by catalytic dehydrogenation into an oligomer or polymer having an extended pi-conjugated electron system. The loaded carrier medium is unloaded in the unloading unit, in particular in a pressure-stabilized chemical reactor, at a process temperature of between 100 ℃ and 450 ℃, preferably between 150 ℃ and 420 ℃, in particular between 180 ℃ and 390 ℃. The process pressure is between 0.1 and 30bar, in particular between 1 and 10bar, wherein in particular metal-containing catalysts, in particular platinum-and/or palladium-containing catalysts, can be used. It is important that the catalyst be able to release the hydrogen that is released from the LOHC carrier medium as hydrogen gas. In addition to platinum and/or palladium, metals such as chromium, iron, cobalt, nickel, copper, iridium or ruthenium are particularly suitable for this purpose.
The utilization unit, which is connected to the separation/purification unit via the first fluid conduit, enables the separated and purified hydrogen to be directly utilized, in particular by generating electricity in an electricity generating unit. The utilization unit may also take different forms to physically utilize the hydrogen gas. The power generating unit is in particular a fuel cell, in particular a PEM fuel cell, having in particular a polymer electrolyte membrane.
The heat conversion unit (in particular the hydrogen burner) connected to the separation/purification unit via the second fluid conduit makes it possible to advantageously increase the overall efficiency of the system in such a way that the residual gas mixture is advantageously burnt and can thus be thermally converted. The residual gas mixture is a substream from the gas mixture in the dehydrogenation unit from which hydrogen has been separated off. The residual gas mixture is in particular not purified and may contain impurities, in particular in the form of hydrocarbon compounds. Such impurities have no problem in terms of thermal conversion of the residual gas mixture. This is based on the discovery that: on the one hand, only partial purification is sufficient for hydrogen power generation in fuel cells, and on the other hand, thermal conversion of the residual gas mixture in the thermal conversion unit is not problematic.
The connection of the thermal conversion unit to the power generation unit according to claim 2 enables an overall efficiency to be increased even more by supplying residual hydrogen (in particular from the fuel cell) to the hydrogen burner. It has been found that the overall efficiency is further improved when the separately purified hydrogen is partially, especially incompletely, used for power generation in a power generation unit. The efficiency of the power generation part is improved, in particular up to 55%, due to the reduced expenditure for generating power in the fuel cell. The actual overall efficiency can be increased to a maximum of 38%. Even if the hydrogen gas flow, i.e., the hydrogen gas flow to be introduced, is fully utilized to generate electricity, the maximum efficiency of the fuel cell is not achieved.
The electrochemical compressor according to claim 3 enables an advantageous separation of hydrogen in a separation/purification unit. The application of a voltage promotes the passage of hydrogen through the separation membrane, while other substances, in particular impurities, cannot pass through the membrane. More particularly by the controlled application of an electric potential, the proportion of the gas stream to be separated can be influenced in a controlled manner, so that the proportion of the separated, purified hydrogen for the power generation unit can be adjusted. More particularly, the required absolute pressure established in the dehydrogenation unit is reduced. This reduces the expense for operating the dehydrogenation unit, thereby additionally increasing the overall efficiency of the system. The required operating pressure of the fuel cell is provided by means of an electrochemical compressor.
The scrubbing unit according to claim 4 is configured in particular as a gas scrubbing unit for separating LOHC components (in particular in droplet form) from a gas mixture. The washing unit is arranged in particular upstream of the heat conversion unit. Additionally or alternatively, the washing unit may be disposed upstream of the separation/purification unit.
The heat transfer unit of claim 5 contributes to further overall efficiency. The heat from the combustion of hydrogen can be supplied directly to the dehydrogenation unit to provide the reaction enthalpy necessary for the release of hydrogen. It is advantageous when the proportion of the residual gas mixture is determined by volume such that the heat generated in the thermal conversion unit is just sufficient to supply the reaction enthalpy for the dehydrogenation. For this purpose, a central control unit can be provided in order to monitor and control, on the one hand, the heat requirement in the dehydrogenation unit and, on the other hand, the separation of hydrogen from the gas mixture in the separation/purification unit. The manipulated variable for controlling, in particular for separating hydrogen from the gas mixture, can be the electrical energy supplied to the electrochemical compressor or the voltage supplied. Additionally or alternatively, the waste heat in the power generation unit may be recycled by means of the heat transfer unit of the dehydrogenation unit.
The advantages of the method according to the invention as claimed in claims 6 to 11 correspond to the respective advantages of the corresponding system, to which reference is hereby made.
The method according to claim 8 can be implemented economically and makes it possible to increase the overall efficiency. The expense involved in pressurizing in dehydrogenation units is reduced. Advantageously, the elevated pressure level in the separation/purification unit is provided by means of pressurization by means of electrochemical compression, so that hydrogen can be utilized in many ways. In addition to using hydrogen in the power generation unit to generate electricity, another option is to physically utilize hydrogen, for example. The hydrogen pressure that can be achieved by means of electrochemical compression is in particular greater than 5bar, in particular greater than 10bar, so that in particular additional compression processes can be dispensed with. The complexity of the device and system technology is reduced. The method is simple and can be advantageously implemented.
The method of claim 9 improves overall efficiency. The expense of providing heat in the dehydrogenation unit is reduced.
The method according to claim 10 advantageously divides the gas mixture into sub-streams. It has surprisingly been found that the overall efficiency of the process can be increased when at most 85%, in particular 80%, in particular at most 75%, of the sub-streams are separated and purified from the gas mixture fed to the separation/purification unit for downstream power generation. The residual gas mixture which has not been separated off can be conducted directly for thermal conversion. Any impurities in the residual gas mixture are not a problem.
The method of claim 11 reduces overall heat demand.
The method according to claim 12 enables an increase in the overall efficiency of the power generation unit, in particular the fuel cell. Since only a portion of the separated and purified hydrogen gas, which has been supplied to the power generation unit for power generation, is controllably used, the overall efficiency of the fuel cell for the portion of power generation is improved. In particular, advantageously, the hydrogen fraction not used for power generation can be supplied directly to the heat conversion unit and used in an energetically feasible manner. It is particularly advantageous if the amount of hydrogen not converted into electricity is at least 5%, in particular at least 8%, in particular at least 10% and in particular at least 15%.
The features specified in the claims and in the following embodiments of the system according to the invention may be independent of each other or combined with each other, enabling further development of the subject matter of the invention. The various combinations of features are not to be construed as limitations on the further development of the inventive subject matter, but are merely exemplary in nature.
Further features and advantages of the invention will emerge from the following description of a working embodiment in conjunction with the accompanying drawings. The figures show:
FIG. 1 is a schematic view of a system for supplying and utilizing hydrogen gas in accordance with the present invention;
FIG. 2 is a schematic diagram of a separation/purification unit in a first working embodiment of the system depicted in FIG. 1;
fig. 3 is a schematic diagram of a separation/purification unit in a second working example (corresponding to fig. 2).
The system 1 shown in fig. 1 and 2 is used for supplying and using hydrogen. The system 1 comprises a first storage vessel 2 in which an at least partially loaded hydrogen-bearing medium is stored in the form of LOHC. The first storage vessel 2 is connected to a dehydrogenation unit 4 by means of a fluid conduit 3. The fluid conduit 3 is in particular a line for conveying liquids and/or gases. The dehydrogenation unit 4 is connected to a separation/purification unit 5 by means of a further fluid conduit 3. The separation/purification unit 5 has a separation membrane 17 for separating from the gas mixture and for purifying hydrogen gas.
The separation/purification unit 5 is connected by means of a further fluid conduit 3 to a power generating unit 6 in the form of a fuel cell. The separation/purification unit 5 is connected to a heat conversion unit 7 via a fluid conduit 3. The heat conversion unit 7 is designed as a hydrogen burner. Along the fluid conduit 3, a scrubbing unit 8 in the form of a gas scrubber is arranged between the separation/purification unit 5 and the heat conversion unit 7.
As for the washing unit 8, additionally or alternatively, a further washing unit 8 (not shown) may be provided upstream of the separation/purification unit 5, in particular between the dehydrogenation unit 4 and the separation/purification unit 5.
The power generation unit 6 and the heat conversion unit 7 are connected via another fluid conduit 3.
The power generation unit 6 is connected to the power consumer 9 via an electric wire 10. The power consumer 9 is arranged to receive and/or use the power generated in the power generating unit 6. The power consumer 9 can be used directly for consuming power. The power consumer 9 may also be a private or public power grid into which the generated power is fed in order to provide current for other consumers connected to the grid.
The system 1 further comprises a heat transfer unit 11, which, according to the working embodiment shown, is connected with the heat conversion unit 7 and the power generation unit 6 via heat conducting pipes 12. The heat pipes 12 are used to carry a heat transfer medium, in particular a heat transfer fluid. The heat transfer unit 11 is connected to the dehydrogenation unit 4 by means of another heat pipe 12 to provide heat.
The heat transfer unit 11 may be connected with the heat storage arrangement 30 to store heat from the power generation unit 6 and/or the heat conversion unit 7 and to be able to make it available at a later specific moment (juncture) in a time-decoupled manner. According to the working embodiment shown, the thermal storage device 30 is integrated in the heat transfer unit 11. The thermal storage device 30 may also be of external design, i.e. in addition to the heat transfer unit 11.
The system 1 also has a control unit 13 which is connected to the components of the system 1 by means of signal lines 14 and which is able to transmit signals to the components of the system 1. The signal conduit 14 is shown in fig. 1 by a symbol of wireless signal transmission. The signal line 14 can also be designed as a cable connection. More particularly, the control unit 13 is connected to the dehydrogenation unit 4, the separation/purification unit 5, the power generation unit 6, the heat conversion unit 7, the power consumer 9 and/or the heat transfer unit 11.
The dehydrogenation unit 4 is connected to a scrubbing unit 8 via a fluid conduit 3. The washing unit 8 is connected to a second storage container 15 via a further fluid conduit 3. The second storage vessel 15 serves for storing the at least partially dehydrogenated hydrogen-carrying medium, in particular in the form of an LOHC. The dehydrogenation unit 4 can be connected directly to the second storage vessel 15 by means of a further fluid conduit 3.
In principle, it is conceivable to provide only a single storage container instead of the first storage container 2 and the second storage container 15. In this case, the at least partially hydrogenated and the at least partially dehydrogenated hydrogen storage medium may be stored in the same storage vessel.
The second storage vessel 15 is connected via a fluid conduit 3 to a hydrogenation device 16. The hydrogenation device 16 is connected to the first storage vessel 2 by means of a further fluid line 3. The hydrogenation unit 16 may also be dispensed with.
If the hydrogenation apparatus 16 is provided, the hydrogen storage medium can be enriched (i.e., loaded) with hydrogen gas and used to release (i.e., unloaded) hydrogen gas during the cycle. It is possible to arrange a circulation arrangement of the dehydrogenation unit 4, the second storage vessel 15, the hydrogenation device 16 and the first storage vessel 2, which are connected to one another in pairs in the above-described order by means of the fluid conduit 3. Especially during high energy periods based on the season and/or depending on the day (especially when the current can be generated by means of renewable energy sources) the current can be generated by insolation or wind power and used for the electrolysis of the hydrogen storage medium in the hydrogenation unit 16 as well as for the hydrogenation. Accordingly, hydrogen in the gas mixture can be supplied by means of the dehydrogenation unit 4, in particular during low energy periods when energy is not sufficient, requiring energy.
The method of supplying and using hydrogen by means of the system 1 is described below with reference to fig. 1. The at least partially loaded LOHC is carried from the first storage vessel 2 via fluid conduit 3 into the dehydrogenation unit 4. In the dehydrogenation unit 4, the hydrogen-carrying medium is at least partially dehydrogenated and thereby releases the gas mixture. The released gas mixture contains hydrogen.
The gas mixture is supplied from the dehydrogenation unit 4 to the separation/purification unit 5 via the fluid conduit 3. By means of the separation membrane 17, hydrogen is at least partially separated and purified from the gas mixture. In particular, the volume flow rate of the separated hydrogen gas represents at most 85%, in particular at most 80% and in particular at most 75% of the gas mixture supplied to the separation/purification unit 5.
The substream of the separated hydrogen has a purity of at least 99.9%, in particular at least 99.99%. The purified hydrogen substream is supplied to the power generation unit 6 via the fluid conduit 3 and converted directly into electricity. The power generation unit 6 is designed as a fuel cell. In a fuel cell, only a sub-stream of the delivered hydrogen is converted into electricity. In the working embodiment shown, the remaining part of the hydrogen not converted into electricity is approximately 10%, which is supplied to the heat conversion unit 7 for heat conversion and combustion therein.
For example, the gas mixture from the dehydrogenation unit 4 can be divided in the separation/purification unit 5 so that 80% of the hydrogen is supplied to the power generation unit 6 as a sub-stream which has been separated and purified. A residual gas mixture with a hydrogen content of 20% is supplied (optionally via a scrubbing unit 8) to the thermal conversion unit 7. The substream with a purified hydrogen content of 80% is used only partially, in particular incompletely, for power generation in the power generation unit 6. The remaining part (e.g., 10%) of the hydrogen gas not used for power generation is supplied from the power generation unit 6 to the heat conversion unit, particularly the hydrogen burner 7, and burned therein. In this version of the method, 70% of the hydrogen content is thus used for power generation and 30% of the hydrogen content is thermally converted, that is to say burnt. The overall efficiency is higher, in particular 38%, since complete power generation in the power generating unit 6 is avoided.
In such a process, the residual gas mixture containing 30% hydrogen is separated in the separation/purification unit 5, and 70% of the hydrogen content in the power generation unit is completely used for power generation. This reduces the efficiency to around 35% overall.
The generated power may be supplied to the power consumer 9 via a power line 10.
After separation of the hydrogen gas, the residual gas mixture discharged from the separation/purification unit 5 is supplied to the washing unit 8 via the fluid conduit 3. In the scrubbing unit 8, the residual gas mixture may be injected from the dehydrogenation unit 4 into the at least partially dehydrogenated LOHC. This releases a drop of residual gas mixture. The residual gas mixture thus purified is supplied from the scrubbing unit 8 via the fluid conduit 3 to the heat conversion unit 7 and combusted therein. The dehydrogenated, that is to say at least partially unloaded, LOHC is conveyed from the scrubbing unit 8 via a fluid line to the second storage container 15. In particular, not the entire flow of LOHC in dehydrogenation unit 4 is required for gas scrubbing in scrubbing unit 8, so a sub-stream of LOHC can be recovered directly from dehydrogenation unit 4 via fluid conduit 3 into second storage vessel 15. The dehydrogenated LOHC in dehydrogenation unit 4 and/or scrubbing unit 8 may be delivered from second storage vessel 15 and/or directly. A transport vehicle (transport vehicle) and/or a transport catheter may be used for continued transport. The dehydrogenated LOHC can also be hydrogenated again, i.e. loaded with hydrogen, in the system 1 by means of the hydrogenation device 16 and supplied to the first storage vessel 2 via the fluid line 3. In particular, a closed circulation system can be provided in the system 1 for the catalytic hydrogenation and dehydrogenation of the hydrogen-carrying medium.
The heat generated in the power generation unit 6 and the heat conversion unit 7 is supplied to the dehydrogenation unit 4 via the heat transfer unit 11 and the heat conductive pipe 12. Thereby reducing the heat requirement for the reaction enthalpy for hydrogen release. More particularly, a separate auxiliary heater may be dispensed with.
The control unit 13 serves in particular to divide the substance flow in the separation/purification unit 5. The control unit 13 is provided so that the flow rate of the purified hydrogen delivered by the separation/purification unit 5 into the power generation unit 6 and/or the residual gas mixture for delivery into the heat conversion unit 7 can be controlled in accordance with the current process parameters. An important factor for the flow rate of the purified hydrogen is the power to be supplied. The key factor for the amount of residual gas mixture is, inter alia, the heat requirement in the dehydrogenation unit.
The structure and function of the separation/purification unit 5 will be described in detail with reference to fig. 2. The separation/purification unit 5 has a housing 18 which is designed substantially cylindrically with respect to a longitudinal axis 19. Housing 18 has a feed inlet 20 for feeding the gas mixture from dehydrogenation unit 4. The fluid conduit 3 is connected to the feed opening 20. The feed opening 20 is arranged in a first end face 21 of the housing 18 shown on the left in fig. 2. On a second end face end 22 opposite the first end face end 21, a residual gas mixture outlet 23 is provided. A further fluid conduit 3 is connected via a residual gas mixture outlet 23 and is connected with the scrubbing unit 8.
On the outer cylindrical wall of the housing 18, a further fluid line 3 is provided which connects the separation/purification unit 5 with the power generation unit 6 and is connected to the hydrogen outlet.
A plurality of separation membranes 17 are provided in the housing 18. For example, the separation membrane 17 is designed as a hollow filament (hollow filament). The mode of action of the separation membrane 17 is based on the principle of selective permeation across the membrane surface.
In order to permeate hydrogen gas (supplied together with the gas mixture from the dehydrogenation unit 4 to the separation/purification unit 5) through the gas membrane, a partial pressure difference of the gas mixture between the residual gas mixture side and the hydrogen gas side is required. The residual gas mixture side of the separation membrane 17 is formed by the inner cavity, i.e., the inner side, of the separation membrane 17. The hydrogen side is formed by the outer sides of the separation membranes 17, i.e. in particular the gaps between the individual separation membranes 17. The greater the pressure difference, the more hydrogen gas permeates through the individual separation membranes 17.
A second working example of the separation/purification unit is described below with reference to fig. 3. Structurally identical parts have the same reference numerals as in the first working embodiment and are described herein with reference thereto. Parts that are structurally different but functionally identical have the same reference numeral followed by an "a".
The essential difference compared to the working example described above is that the separation/purification unit 5a has an electrochemical compressor 25 in addition to the separation membrane 17. The electrochemical compressor 25 includes a power source 26 connected to an anode 27 and a cathode 28. A separation membrane 17 is provided between the anode 27 and the cathode 28. Anode 27, cathode 28 and separation membrane 17 are disposed inside housing 18. On the side of the anode remote from the separation membrane 17, a feed opening 20 and a residual gas mixture outlet 23 are provided in the housing 18. The hydrogen outlet 24 is provided on the side of the cathode 28 opposite the separation membrane 17 in the housing 18.
The mode of action of the separation/purification unit 5a corresponds substantially to that of the first working example. The principle of action of the fuel cell is essentially reversed due to the additional application of voltage by means of the power supply, which means that hydrogen is transported from the anode 27 to the cathode 28 via the separation membrane 17. All other substances, in particular impurities in the gas mixture, cannot permeate through the separation membrane 17. The purification of hydrogen is integrated and thus simplified. Since the voltage serves as an additional driving force for hydrogen permeation, the mechanical part pressure selected can be small and in particular mechanical part pressure differences can be dispensed with. This makes it possible to reduce the absolute pressure in dehydrogenation unit 4, so that it is possible to release hydrogen, in particular in the range of 1.0bara to 1.5 bara. The process temperature is at least 200 ℃, in particular between 240 ℃ and 320 ℃.
This example of application can be used in particular in hydrogen station applications. A particularly advantageous implementation for supplying hydrogen is ensured by virtue of the combination of the dehydrogenation unit 4 with an electrochemical compressor as separation/purification unit 5 and with the thermal conversion unit 7 for continuously supplying gaseous hydrogen to the hydrogen gas station. This can be operated without additional purification steps and external energy supply, in particular in the form of electricity for heating. The gaseous hydrogen has the purity required for the application and the pressure level required for further compression to between 350 and 700bara to aerate an automobile, bus or carrier vehicle.
According to the working embodiment shown, the separation membrane 17 has an upstream conditioning device 29. The regulating device 29 serves to regulate the gas stream supplied to the separation/purification unit 5a with respect to the separation membrane 17, in particular to control the moisture content. According to the working embodiment shown, the regulating device 29 is a device for controlling the humidity of the supplied air flow. The adjusting device 29 can also be dispensed with. The regulating device 29 may be used to influence other physical properties of the gas flow, such as the temperature.
The adjusting device 29 is arranged in its entirety inside the housing 18 in the region of the feed opening 20. The conditioning device 29 can also be designed as an external component connected upstream of the separation/purification unit 5 a.
Typically, the potential difference between anode 27 and cathode 28 is about-0.03V.
Claims (12)
1. A system for providing hydrogen gas comprising
a. A dehydrogenation unit (4) for releasing a hydrogen-containing gas mixture from the at least partially loaded hydrogen-carrying medium,
b. a separation/purification unit (5; 5a) connected to the dehydrogenation unit (4) for at least partially separating hydrogen from the gas mixture and for purifying the separated hydrogen, wherein the separation/purification unit (5; 5a) has a separation membrane (17),
c. a utilization unit (6) connected to the separation/purification unit (5; 5a) for utilizing the purified hydrogen,
d. a thermal conversion unit (7) connected to the separation/purification unit (5; 5a) for thermally converting the residual gas mixture.
2. The system according to claim 1, characterized in that the utilization unit, in particular the power generation unit (6), is connected with the heat conversion unit (7) for supplying an exhaust gas flow from the power generation unit (6).
3. The system according to any one of the preceding claims, wherein the separation/purification unit (5a) has an electrochemical compressor (25).
4. The system according to any one of the preceding claims, characterized in that a scrubbing unit (8) is provided for scrubbing the residual gas mixture from the separation/purification unit (5; 5a), wherein the scrubbing unit (8) is arranged in particular upstream of the heat conversion unit (7).
5. The system according to any of the preceding claims, wherein a heat transfer unit (11) is provided for recovering heat from the power generation unit (6) and/or from the heat conversion unit (7) into the dehydrogenation unit (4).
6. A method for providing hydrogen, comprising the method steps of:
-releasing a gas mixture comprising hydrogen from the at least partially loaded hydrogen-bearing medium by means of a dehydrogenation unit (4),
-at least partially separating hydrogen from the gas mixture and purifying the separated hydrogen by means of a separation/purification unit (5; 5a) connected to the dehydrogenation unit (4),
-wherein at least partial separation of hydrogen from the gas mixture and purification of the separated hydrogen is effected by means of a separation membrane (17),
-converting the purified hydrogen into electricity by means of a utilization unit (6) connected to the separation/purification unit (5; 5a),
-thermally converting the residual gas mixture by means of a thermal conversion unit (7) connected to the separation/purification unit (5; 5 a).
7. The method of claim 6, wherein the separated hydrogen is purified by electrochemical compression.
8. A process according to any one of claims 6 or 7, characterised in that the hydrogen-containing gas mixture is released at an absolute pressure in the range 1.0 to 3.5bara, especially 1.0 to 2.0bara, more especially 1.0 to 1.5 bara.
9. The method according to any one of claims 6 to 8, characterized in that the gaseous mixture containing hydrogen is released at a temperature of at least 200 ℃, in particular in the range of 240 ℃ to 320 ℃.
10. The method according to any one of claims 6 to 9, characterized in that at least part of the separation is such that the hydrogen production rate based on the gas mixture supplied to the separation/purification unit (5; 5a) does not exceed 85% by weight, in particular does not exceed 80% by weight, and in particular does not exceed 75% by weight.
11. The method according to any of claims 6 to 10, characterized in that heat from the power generation unit (6) and/or the heat conversion unit (7) is recovered into the dehydrogenation unit (4).
12. The method according to any one of claims 6 to 11, characterized in that the utilization unit is designed as a power generation unit (6), the purified hydrogen supplied to the utilization unit being used only partially for power generation, and the remaining hydrogen gas stream that is not used for power generation being discharged in particular from the power generation unit (6) and in particular supplied to the heat conversion unit (7).
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE102017217748.9A DE102017217748A1 (en) | 2017-10-05 | 2017-10-05 | Plant and method for the provision and further use of hydrogen gas |
| DE102017217748.9 | 2017-10-05 | ||
| PCT/EP2018/072183 WO2019068387A1 (en) | 2017-10-05 | 2018-08-16 | System and method for providing and further using hydrogen gas |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN111212810A true CN111212810A (en) | 2020-05-29 |
Family
ID=63244614
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201880065003.XA Pending CN111212810A (en) | 2017-10-05 | 2018-08-16 | System and method for supplying and further using hydrogen |
Country Status (5)
| Country | Link |
|---|---|
| EP (1) | EP3691989B1 (en) |
| KR (1) | KR102549839B1 (en) |
| CN (1) | CN111212810A (en) |
| DE (1) | DE102017217748A1 (en) |
| WO (1) | WO2019068387A1 (en) |
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| CN112201812A (en) * | 2020-10-10 | 2021-01-08 | 上海捷氢科技有限公司 | Fuel cell system, and gas supply method and gas supply device therefor |
| CN115768717A (en) * | 2020-07-10 | 2023-03-07 | 阿科玛法国公司 | Process for improving the quality of organic liquids with hydrogen |
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| DE102018221447A1 (en) * | 2018-12-11 | 2020-06-18 | Friedrich-Alexander-Universität Erlangen-Nürnberg | Process and installation for releasing gas from a liquid medium |
| KR102526670B1 (en) * | 2020-11-20 | 2023-04-27 | 전남대학교산학협력단 | Environment- Friendly Electric Boat Equipped with H2 Evolution Module |
| DE102020215444A1 (en) | 2020-12-07 | 2022-06-09 | Hydrogenious Lohc Technologies Gmbh | Process and plant for the material use of hydrogen |
| DE102021200978A1 (en) | 2021-02-03 | 2022-08-04 | Hydrogenious Lohc Technologies Gmbh | Process and system for releasing a chemically bound component from a carrier material |
| DE102021202170A1 (en) * | 2021-03-05 | 2022-10-20 | Hydrogenious Lohc Technologies Gmbh | Method and system for providing purified hydrogen gas |
| DE102023201170A1 (en) | 2023-02-13 | 2024-08-14 | Hydrogenious Lohc Technologies Gmbh | Method and device for providing electrical current |
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Also Published As
| Publication number | Publication date |
|---|---|
| EP3691989A1 (en) | 2020-08-12 |
| WO2019068387A1 (en) | 2019-04-11 |
| KR102549839B1 (en) | 2023-06-29 |
| EP3691989B1 (en) | 2024-09-11 |
| KR20200066331A (en) | 2020-06-09 |
| DE102017217748A1 (en) | 2019-04-11 |
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